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·~
THE
D~TECTION
OF POISONS IN THE PRESBNCE OF . " ---.
I
I
mrnALWl:ING FLUID
.
by
Paul E. Laird
A thesis
submi~ted
to the
De~artment
of Chemistry
and the Faculty of the GrR.duate School
in -partial fulfillment of the
requirements for the
Master's Degree
Denartment of Chemistry
INTRODUCTION
1
INTRODUCTION
Classification.:Nearly all of the common poisons and
drugs may be placea in one of the three groups.The following
poisons with their .classification were used in this thesis;
Grou:p I.-The members. of this group volatilize with
out decomposition when heated and distil from an acid solution
with steam. :Potassium cyanide,hyorocyanic acid,carbmlic acid
and chloral hydrate.
Group II.-The members of this. group are non-volatile,
organic substances which do not distil from an acid solution
with steam.Hot alcohol containing tartaric acid will extract
them from foreign matter.Alkaloias,many glucosides and bitter
principles,as well as certain synthetic organic drugs like
acetanilide and antipyrine comprise this group.
Group III.-This group includes all of the metallic
poisons such as arsenic,mercury,etc.
Purpose.-The reason for writing this discourse and·
the making of thorough analyses of a number of poisons in the
presence of embalming fluid,is that each year a number of '
deaths occur which may be homicidal,suicidal or accidental
which require a thorough chemical investigation to meet the
requirements of the law.Under the ordinary conditions of today,nearly all bodies are embalmed immediately after death
with.one of the standard embalming fluids.
In
most of the
states,the embalming fluids are free from certain metallic·
poisons,yet when a case is brought into court,it is necessary
to prove to the satisfaction of the jury that the poison
~ound
in the body after death was not due to the embalming
2
fluid.Then it is the object of this thesis to show what effect
if any that embalming fluias have on poisons which have been
taken into the body.
Experimental .-In the preparation of the samples for
analyees 9 conditions were brought as nearly as possible to
those found in the average case. The analysis in every case
was followed carefully that no error might exist which would
obscure the results.The amount of poison used in each sample
was below the lethal dose. Being such a small a.mount, it would
clearly show any effect that the embalming fluid might have
·on the poison and at the same time it would show any combined
action of the embalming fluid and cadaver on the poison.
Embalming fluids used.- In the selection of embalming
fluids,those were selected which were standard and very generally used. Champion Embalming Fluid and the Dioxin were the
,
two used. A partial analyis of each shaus as follows:
Champion Embalming Fluid as used by the embalmer:
Dioxin
as~
Fromaldehyde
5.1 per vent.
Glycerine
3.1 per cent.
Borax
0.39 per cent.
Uf:?ed by the embalmer:
Formaldehyde
6.4 per cent.
Glycerine
1.53 per cent.
Borax
0.02 -per cent.
T.A:BLE OF CONTENTS
Page
Prenaratio n of reagents and solutions
3
Potassium Cyanide
6
Phenol
12
Chloral Hydrate
16
Acetanilid e
21
.Anti-nyr ine
24
. Caffeine
2'7
Veratrine
31
Strychnin e,
34
Brucine
39
Atronine
42
Aconite
46
Cocaine
50
Codeine
54
Narcotine
5A
Quinine
61
Mornhine
65
Arsenic
'70
3
J?REJ?.ARATION OF REAGENTS .AND
SOLU~IONS
General Alkaloidal Reagents.- A class of reagents,
known as general alkaloidal
r~agents,as
per Autenreith,added
to solutions of most of the alkaloids or their
sal~s,produce
precipitates which are characterized by their color or in
the' appearance of the precipitate. These reagents do not .precipitate the alkaloids ·exclusively. They are especially useful in detecting the presence or absence of alkaloids and
othe·r basic compounds. If there is only a slight residue :from
the ether extract of a1ka1ine solution in the Stas-Otto method,
test first with the general alkaloidal reagent and then,if
necessary,for the genera1 alkaloids or the individual.To perform these tests dissolve the residue in dilute hydrochloric
or sulphuric acid,distribute the filtered solution upon watch
glasses and add to each portion a drop of the more sensitive
reagents. If an alkaloid or any other basic suhstance is present, distinctive precipitates or at least decided cloudiness
will appear in all or nearly all of the tests.
The most important general alkaloidal.reagents are
the following:
Mercuric Chloride dissolve.a in
wat~r
(l: 20) produces
white to yellowish precipitates which are usually amorphous
but gradually become crystalline.
Iodo-J?otassium Iodide,prepared by dissolving 5 part·s
of iodine and 10
~arts
of potassium io[ide in 100 parts of
water,produces brovm precipitates which are
usuall~
flocculent.
4
Tannie Acid,is a 5 per cent,aqueous solution of tannin.
This reagent produces whitish or yellowish precipitates partly soluble in hydrochloric acid.
l?icric Acid in a concentrated aqueous solution produces yellow crystalline precipitates.
Erdmann's Reagent.-Sulphuric acid containing nitric
acid,prppared by adding to 20cc.of pure concentrated sul_phuric .adid,10 drops of a soultion of 6 drops of concentrated nitric acid,in 100 cc. of water.
Froehde's Reagent.- A solution of molybdic acid in
sulphuric acid, prepared by dissolving 5mg. of molybdie acid,
or sodium molybdate,in lee.of -hot pure concentrated sulphuric
acid. Thsi solution,which should be colorless,does not
~eep
long.
·Fehling'sSolution.-The two following solutions,which
should be kept separate, are used in
prepar.~:ing
this reagent:
i.· Copper sulphate,made by dissolving 34.64 grams
of pure copper sulphate in sufficient water to ma.k.e 500cc.
· 2. 'Alkaline Rochelle salt solution,made by dissolving
173 grams of Rochelle salt and 50 grams of sodium hyuroxide
in.hot water and diluting to 500cc.
These two solutions,mixea volume for·volurne,constitute Fehling's dolution.They
mng used.
sho~ld
be mixed just before be-
'
Formaldehyde-Sul-,huri~c
Gunzburg' s
.
using~
ReA.gent~-
........
,,
-
-·
·- · - ·
Acid. -Add 3 drons of an
ous formaldehyde solution to a few
sulnhuric acid just before
_, -
'
-~-·-. -
·~
i
aoue-
drops of nure concentrated
,
Dissolve 1 uart of nhlorogluc-
inol and l part of vanillene in 30 narts of alcohol. This
reagent is used to detect free mineral acids,esnecially hydrochloric~but
it does not react with free organic acids.
Iodic Acid
Solution.-Pre~are
a 10 ner cent.solution
of iodic acid.
Millon's Reagent.-Dissolve one µart of mercury in
one
~art
of cold fuming nitric acid. Dilute with twice the
volume water and decant the clear solution after several hours.
N~ssler's Reagent~-
Dissolve senarately in the cold.
3.5 grams of potassium iodide in 10 cc.of water.Add mercuric
chloride s.olution. 30cc . containing 1. 'l grams of mer curio chloride. Add the mercurice chloride solution to the uotassium
iodide solifltion unt.il there is a permanent 11reci-pitate. Dil.ute with 20 uer cent solution of smdium hydroxide to lOOoc.
Add the mercuric chloride soltuion.until there is again a
nreoinitate and let the solution settle.
Stannous Chloride Solut'ion.- Mix 5 grams of stannous
chloride with one nart of hydrochlorie acid and then saturate
with dry hp-drochloric acid gas.
6
:POTASSim:T CYANIDE
Potssium
,c~aninde
is present in numerous plants e.g.
in laurel leaves, bitter almonds,cherry and
~each
kernels us-
ually in combination with glucose and benzaldehyde as the
glucoside
amy~dalin,which
is hydrowized by acids,or·enzymes
in the ulants,into its constituents.Hydrogen cyanide resembles
hydrochloric acid in
behav~or,
forming salts with alkalies
ana
metalli« hydroxides.
The chief salt is uotsssium cyanide which is used
exeensively for extracting gold and in electroplating.It is
rirepared by fusing notassium f:errocyaniae.Large quantities
of cyanide are now nreparea in two methods:
(1). by heating sodium with charcoal in a current of
ammonia at 400 degrees. Sodamide is formed and convertea into
sodium cyanamide.
'(2) .by heating beet sugar molasses to 1000 degrees.
At this temperature the trimethylamine is decomnosea into
hydroc¥ anic acid and methane.
The metallocyanides,such as notassium
ferrooyanide~
Prussruan blue,etc. are usually considered non-toxic.Several
1Jrominent chemists ex-iierimentea with them on aogs and guinea T)igs and failec1 to obtain -poisonous effects. The thiocyanates ·of sodium ana.' ammonium are usually considered non-<
toxic,ana Pollak has shown that they are almost quantitatively
eliminatea unchanged in the urine.
Stati.stics.-Rydrocyanic acid was discovered by
Scheele in 1870. There have been many cases of accidental
noisonings of recent years where the cyanides have been used
in the arts. Of 492 cases of cyanide noisonings
whi~~
:.1h Wi tthaus
classified,194 were by hydrocyanic acid,154 byuotassium
cyanide,65 by oil of bitter almoTI:ds,etc •. The greater
n~rtion
of the oases were suicidal and were mostly nharmacists,nhysioians or chemists. Although cyanide noisons have a pronounced
oaor,yet there have been many cases of homicide by its use.
Lethal Dose.-The minimum lethal dose of uotassium
cyanide is difficult to fix with certainty,owing to the
varying strength.It is urobable thht even so small a quantity
as 0.05 grams of 'the anhydrous acid might urove fatal.
Absorntion.- Va11ors of HCN are very ranidly, absorbed
by the lungs. Both the acid and YCN in 'solution are ran idly
absorbed from all surfaces.even from the uninjured skin,as
well as from the eye when
re~niratory
absorption is prevented.
Analysis.-Owing to the great volatility and instability of BCN,the probability of its detection in the cadaver diminishes ra1)iclly as time ela1)ses, 11articularly if the condition
favoring uutrefaction
obta~n.My
tests with KON and meat
~how
clearly how the -put1rnfaction diminishes the amounts detectable.
What the reactions are that go one in the body are problematical and authors differ.It is nossible that RCN is convertea
into thiocyanates during life,but it also might condense with
8
oarbohydrates,ana during nutrefaction,be hrydolized into annnonia formate,and by these means escape detection.
In a systematic analysis for all noisons HCN would
anpear, if -present, either free er in combination exce11t mercuric cyanide, in the first distillate obtained in the search
for volatile -Poisons to ·which the tests below described anply.
This method should not be used,however,when circumstances
noint clearly to cyanide uoisonings,as metalocyanides,such as
thiocyanates normally uresent in the body,ana notassium ferrocyanide may yield free HCN on distillation with mineral acids.
When I treated a nncmti ty of meat with embalming flui9.
containing KCN,I was unable to get any cyanide test by distillation with tartaric acid.I boiled the meat which had been
treated with embalming fluid containing RCN with sodium hydroxide for some time and then made it acid with
tart~rio
acid and
distilled,yet I got no test for cyanide.
It was suggested that if theoyanide was dissolved
in embalming ·fuid made acid the strength
og gastric juice
it could b.e detectea .I made embalming fluid acif with HCl
to the extent of 0.5
~er
cent HCl and then dissolved the
KCN 1n the acidulated emba'J_ming fluid.I could get no cyanide
test by either method: direct treatment with tartaric acid "
ana 'distilling or by first boiling ·with sodium hydroxide and
then
acid~latirtg
and
There are
aistil~ing.
many
nossible exolanations which tend to
show the reason for the d isaunearance of the cyanide .,Schimpf
9
says that the notassium cyanide unites mole for mole with the
formaldehyde to form an addition nroduct as:
H
CH2 0
+
KCN -:::-
I
N=c-c-c-x
~
l
H
I tried many methods by which I honed to break up ·
the 11roduots and liberate the cyanide, thereby. enabling me
to get a cyanide test.I was unable ·to accomnlish the task.
I made a serees of analyses to show the effect of
decomnosition of meat unon potassium cyanide.
Detection.After each treatment and distillation it
was necessary to
aD~ly
the fo1lowing tests.
GuA.iac Test. - Moisten a niece of filter pan er with
freshly
~renared
three-ner-cent.alcoholic solution .of guaiac
then dry and moisten with a drop of
o.o5
~er
cent. solution
of cur>ric sulnhate, and then with a dro;;> of the susnected solution. In the nresence of hydrocyanic acid a beautiful blue
color is uroducea.. Other substances than HON will give this
test.
Prussian Blue Test.- Add to the distillate a little
potassium hydroxide solution, then a fe\"l drops of ferrous sulnhate and one
drou- of ferric chloride solution.Shake
well
.
.
.
and warm gently. Finally acidulate with dilute.hydrochloric
acid.If
much
HON is present,a "Precinitate of :Prussian blue
.
will appear,If the quantity
is small,the solution will have
a blue or blue green color.Limit of delicacy l : 1.500.000.
10
Silv er Bit rate Tes t.- Aci dify a nor tion of
the distill ate wit h dilu te nit ric ac,ia and add silv
er nitr ate solutio n in exc ess .If HCN is pre sen t.a whi te.c
urd y nre cin itat e
wil l aun ear . Exc ess of ammonium hyd roxi de
solu tion wil l
rea dily diss olv e this ~reoinitate.
Quna.ti tati ve esti mat ion of nota ss ium c~.n
ide. - To
dete rmi ne KCN qua ntit ativ ely ,aci dify a weig
hed .nor tion o~
mat eria l,ac idif y
with dilu te sul~huric acid or tart aric and
dis till . Det erm ine the qun atit y of E.CN gra
vim etri onl ly by
the ~recinitation of the cya nide
as silv er cya nide ana
wei ghin g.
S-p ecia l.-
Jou rnal Bio log ical Che mis try Sen t . 191 3.
. arti cle by
Dr . H.P .Caa y,D r.E. H. .. S.B aile y and R.VJ.Emerso
n.
The que stio n aros e dur ing the 1)ro gres s· of
a crim inal
tria l whe ther d.ec.orimosi ti on of ,,ro te ins cou
ld und er any con diti ons ~iberate hyd r.oc yan ic acid .
They used in
The ir con clus ions wer e:
thei~
exp erim ents the whi te of an egg .
(&) .Ce rtai n mic roor gan ism s· livi ng on pro tein
med ia
evo lve hyn rocy anic acid .
(b·) ·Th ese orgr u:is ms ;Lib erat e hyd rocy anic
acid bes t
when pro tein is slig htly acid . ·
(c). The y ~o not libe rate hyd rocy anic acia
in media.
con tain ing free min eral acid s.
11
Data ..·Sam~le
containing finely ground liver and
notassium cyanide.The cyanide used was eouivalent to a
76.9 ner cent nure KCN. 200 grams of meat.200 grams of
water and 2 grams of KCN were mixed together and were
subjected to decomnosition changes.
40 grams
of the
samnle were used in each analysis.The samnle was nrenared
June 3,1920.Analysis shO\vn below,
June 4,
O .32~0 grams .AgCN eauals
0"1515 grams KC:H
June 5,.
0.0523
n
n
Q.0254
TT
June 6,
0 . 032!08
TT .
n
0~0152
ff
J1ll1e.7,
0.5533
n
0.0171
"
June 8,
OA0320
n
Q,0155
"
n
June 9.
0.0236
TT
0.0114
"
"
June 16,
"
0.0214
n
"
0.0104
TT
"
June 28.
O.OOR8
"
n
0-0043
n
n
July 6,
m~ace
"
"
Tf
n
"
July 14,gave no Prussian olue test.
TT
"
13
~HENOL
Phenol, Ct,Hs-OH, is obtainea by fusing benzene sulhhonio acid with caustic
~otash~
decomnosi ti on of diazonium
salts~
It is also obtained by the
It i_s contained in coal tar
and is ·present in the . mictdle section. ···When rmre it crystal-.
lizes in long neeiles.which assume a red color on exnosure,
fuses at 43 and boils at 183
degrees~has
a characteristic
odor and an acrid,burning taste.soluble in 15 uarts of water
a,t 20 degrees and is very soluble in alcohol and ether.
The greater majority of phenolic acid noisonings are
~reduced
by carbolic acid itself. a substance whose toxic
oualities are wel+ known,which is accessible to any one ana
which is used extensively as an antiseutic.
Lethal Dose.- Cases are reuorted in Witthaus where
a. nerson died from taking 1.5 grams of phenol and where others
died after taking as little as 3 grams.
Distribution.- Probably because of the small number
of medico-legal investicgations on phenol noisonings,the
dat~.
concerning its distribution in different organs and the duration of its detectability after death are meager.
Prenaration of
Sam~le
for .Analysis.-The.
sam~les
for
analyses were urenared by dissolving a small amount of 1'.)henol
in embalming fluid and then treating meat with it.
Extraction.-Phenol distils quite easily with steam.
Yet,to remove the last traces.long continued distialltion is
necessary.The method usea in all of my analyses in this work
was steam distillation
13
- ·- .......·-...... - ........ ·- _ - ...
Estimation.- The nhenol is extracted by steam distil...
··~·
lation and then nreoinitated from the distillate as tribromnhenylhynobromite by an
of saturate bromine water.The
e~aess
nrectpi tate is 1}ractically insoluble in saturated bromine wa.ter
and the results are farily satisfactory. Th e a.queous "Phenol
solution is ulaced in a large glass sto1:mered bottle and treated
with bromine water. It is necessary to add an excess of bromine water and shake at frequent interuals. The
~reci~itate
is dried in a vacuum desiccator and weighed. The calculation
of the results is 'on the following basis.
. ..
CbF..:s--OH
94.05
Weight "Crpt.
x
The weight of the nhenol may be found by multinlying the
I
weight of the·precinitate by 0.2295.
Detection.- Usually phenml can be recognized by
its neculiar
distillate
odor.~
fo~
The folowing tests were anplied to the
identification •
. ]i!illon's Test.-Itillon's reagent.heated with.a sol-·
.·
ution containing a trace of'nhenol.nroduoes a ~ea color.It
is a very delicate test,but not characteristic of nhenol.
because other aromatic compounds behave similarly •.
Bromine ITater Test.- Excess of bromine water nrod~ces
a yellow precinitate. This is a delicate test one
· uar·t in fifty thousand.
Ferr1.c Chloride Test. - Dilute ferric chloride solution gives a blue-violet color to a nhenol solution.It is
negative in the nresence of mineral acids.
14
.,, ... ~
·-·
I
Hypochlorite Test.- A little ammonium hydroxide
·,
added to a little dilute nhenol solution ana then a little
freshly nrenared hynochlorite solution gives a blue color.
ord~r
to determine the effect of the
~henol.a
series of exPeriments were.run
Analyis.- In
embalming fluid on
with the two together. After finding. that the embalming fludi
had no a~preaiable effect on phenol,a series of analyses were
.
run with embalming. fluid,nhenol and finely ~round meat.
'
Data.-
I.
Samnle containing embalming fluid and phenml.
lOOco.
Embalming fluid,
Phenol,
(a)
2
grams.
One half of the samnle taken for analysis •
Dish plus npt.
Dish
P11t.
2.2681
x
0.2295
=- 0.5205
. 56'. 3915
54·.1234
2.2681
grams nhenol
(b). The remainder of samn1e analyzed 10 days later .
. Dish nlus nnt.
Tiish
:P-nt.
2.1072
x
0.2295
=-
58-.1652
56'. 0580
2.1072
0.4835 grems nhenol.
II.
Samule prenared March 19,1920.as follows:
Embalming flui.d,
80 cc.
Ground meat,
80 grams.
Phenol,
l gram.
15
.....
(a) .March 26,Sam11le .. taken for analysis,40 grams.
~
Dish nlus put.
Dish
:ent.
0.9059
x
0.2295
.,..
........ ,,. --
45·.3559
44·.4500
0.9059
0 . 2079 grams nhenol.
(b).. Anril 8.Samnle taken for analysis,40 grams.
Dish ulus pnt.
Dish
P-pt.
0.94?2
x
0.2295
44·. 5582
43·. 6110
o.9472
. 0. 21 ?2 grams phenol.
(c). Anril 19.Samnle taken for analysis,40 grams.
Dish "Plus npt.
Dish
Put.
0.95?8
x
0.2295
41!·. 5868
43·. 6110
o.9758
0.2231 grams nhenol.
III.
Samnle µreuared June 3,as follows:
Embalming
lOOcc.
~luid,
Ground meat,
100 grams.
Phenol,
2 grams.
(e). June 10,Samnle taken for ana.lysis,50 grams.
Dish ulus rrpt.
Dish
Pnt.
1.2535
(b). June
x
19,Sam~le
0.2295
0.287? grams phenol.
taken for analysis,50 grams.
Dish µlus ppt.
Dish
P'!"lt.
0.9025
x
57·.3115
56·.0580
1.2535
Q.2295
55'. 0259
54·.1234
0.9025
0.20?1 grams nhenol.
<fo).July 8.,Samnle taken for analysis,50 grams.
Dish ulus upt·.
Dish
Phenol
56'. 9215
56·.0580
o.8635~
Q.1982 gm.'!1hendl.
16
CHLORAL HYDRATE
Cha1oral hydrate, CC1 3 CH(OH) 2 ,is a white crystalline
solid,which melts at. 51 degrees. It . is soluble in 1.5 times
its weight of water.,also in alcohol,ether and carbon di-sulnhide. It i.s soluble with difficulty in cold chloroform
and
distils very slowly with steam from acid solution.There:fore
the comnlete distillation of large quantities of chmoral
hydrate requires considerable time. Chloral hydrate
an~ears
as such in the distillate. It is decomposed with tlie '.lib eration of chloroform by alkalies as by
~his
CCla CH(OH)2. +KOH
2
equation:
= HCOOK+H 0 1"" CHC1
3
Statistics.- Although the use of chloral hydrate as
a medicine was first suggested by Liebreich in 1869,a fatal
suicide by its use occurred .in 1870, ana sine that numerous.
cases have occurrea. I coulc1 find no case where chloral hydrate
had been ministered to ~thers with intent to kill.but it has
been used for the uurnose of fostering other crimes.
Lethal
Dose.~
The
e~fect
of chloral hydrate vary
greatly with different individuals and in the same individual
at different time·s . Death has resul tea .from a less dose than
those
'.
nr~scribed
by 11hysioians. The med:i.oinal dose is from
0.6 to 2 grams,with.a maximum of 5 grams.
Distribution.-Chlora.1
hydrate
.
. is converted into
urochloric acid. nerhm1s in the liver, and anuears a.s such.
1'7
..
in the urine. In the alimentary canal the search should
ohlora~
hydrate. It is very
~rone
b~
for
to decomnosition and in the
cadaver after ingestion during life.it will ran idly d isa:npea.r
a.s 1,utrefaction advances.
Prenaration of Sample for Analysis. - The samnles for
ap.alyses were nrenared by dissolving some chloral hydrate in ·,
embalming fluid and then treating some meat with the solution.
Extraction.- There are tow methods that I usecJ .F1.~st·,~ · ·· ·
I made the solution acid and· distilled with steam for some
time and then made the distillate acid with sulnhuric aci.d
I found this method more
ana extractea with chloroform.
..
satis~
factory than the ··second. while my results were somewhat
what they should have been. yet I
consider~d
below.
them fair. Seconq... ·
the material was heated on the steam bath with a reflux condenser for more than 12 hours with its own weight of 20 ner
cent.nhosnhoric acid. Then to comnlete the
~decomnosition
of
the chloral hydrate into chloroform and formic acid.add 50cc
of sodium hydroxide solution to the distillate and evanorate
to a small volume on .the water bath. The .solution is
neutraJ.-
ized and heated for six hours with an excess of mercuric chloride solution. Finally weigh the nrecinitated mercurous chloride. I found my results too high in the
seco~
method.whether
it was. due to some of the chloroform ·."Qeing changea··ll. to formic
acid or whether it was due to the formaldehyde in the embalming fluid I em not certain.
. 18
··•
• -··
I
Dete6tion.-Chloral Hydrate like chloroform will give
the nhenylisooyanide.resoroinal and Lustgarten's nanhthol
tests .But the d istil·late containing chloral hydrate does not
have the characteristic odor of chloroform which is scarcely
nercentible in dilute aqueous chioroform so~utions.
Nessler's Solution Test.-Add a few drons of this
reagent to an aqueous chloral hydrate solution and shake.It
nroduces a yellowish red
nreci~itate.
The color ·changes in
time to a dirty yellowish green. A few dFops of -potassium
hydroxide changes the color to brownish red .
Chloroform Test.- Eistill a few drops from the solution ·in the flask and test for chloroform by the nhenyliso. cyanide test.
Formic Acid Test.- Filter the residue from the distillation and concentrate to a small volume and test with
mercuric ch:J.oride which will form a white nrecinitate or treat
it \Vi th silver nitrate which will also give a urecini tate of
metallic silver.
Analysis.- A samule ·containing embalming fl':-i:id and
chloral hydrate was analyzed to see what effect if any resulted. A series of analyses were then run in which embalming
I
fluid.chloral hydrate and ground meat were mixed. Two methods
were used in the analyses.In the first series,I used steam
distillation and ether extraction,while in the secong,I used
the reduction of mercuric chloride.
10
~
....... · . '
,
i
Data.I.
Samule containing·embalming fluid and chloral hydrate.
lOOcc.
Embalming fluid,
o.5 grams.
Chloral hydrate,
(2).IDne
hal~
of the
sam~le
taken for analysis.
Dish -plus chloral hydrate 56'.215'7
Dish
.
56'• 0615
Chloral hydrate
0.1542
...
(b). The remainder of the sam11le taken for analysis 10 days lataDish 'Plus chloral hydrate 56·. 2149
Dish
56'. 0580
Chloral hydrate
0.1569
II.
Samnle
~renared
March 19,1920 as follows;
Embalming fluid,
soac.
Ground meat,
80 grams.
Chloral hydrate,
1.5 grams.
(a) .March 25. Saml'.')le taken for analysis, 40 grams.
Dish ·plus chloral hydnate 32·.4856
Dish
32·. 2984
Chloral hydrate
o.1872
(b).Anril 15,S81D.ule taken for analysis,40 gnams.
Dish Plus chloral hydrate 32·.$600
Dish
·32~2984
Chloral hydrate
0.1616
(c). Auril 26,Sam-ole taken for analysis,40 gnams.
Dish plus chloral hydrate 32·. 3996
Dish
32.• 2984
Chloral hydrate
0.1012
20
III.
Samnle nrenared June 3,1920,as follows:
Embalming fluid,
lOOco.
Ground meat
lOOgrams
0.5 grams.
Chloral Hydrate
(a). June 9.Samnle taken for analysis,50 grams.
54·. 7297
54·.1234
0.6063
Dish Plus HgCl
Dish
HgCl
0.2130 grams Chloral hydrate
0.6063 grams HgCl
CCl, CH ( OH)2
HCOOX
+
+
KOH -::.. CHCl 0 -t HCOOK -t H 2 0
2HgCl.i. ==- 2HgCl
2HgCl
+ 002. + HCl + :KCl
Weight HgCl
CC13 ?H(OH) 1
x
(b)Q June 20,Samu+e taken for analysis,50 grams.
54·. 8820
Tiish 'Plus HgCl
54·.1234
Dish
RgCl
0.7586 grams HgCl
o.?586
~
0.2681 grams Chloral hydrate •
.
'
(c). July 14,Samole taken for analysis,50 grams.
Dish nlus sample
D])$h
RgCl
o·.5054 grams HgCl -
54·. 6288
54'.1234
o.5o54
0.1924 grams Chloral hydrate.
21
ACETANIT.:ITIE
Aoeta?_lilide,
c, Hs1ra.co. CH3
, crystallize~
and inodorless . ehinii:g leaflets. It he,s a
in colorless
faint,b:irnin~
taste.
melts at 113 degrees. is soluble in 230 narts cold. 22 narts of
I
.
l
hot water and in 3.5 -narts of alcohol.It is freely soluble in
ether and chloroform.Being an aniline
has the poisonous
~rouerties
derivative~acetanilide
of that amine though in a less degm
Lethal Dose. - R. Kobert ( "Intoxi ka.tionem 11 l refers ·to
several instances of acetanilide noisonings which did not tesult in death. In one case a student took a teasnoonful of
acetanilide. Vlhile he re.covered in several days·. yet he suffered
..
from exhaustion, Similar
who took
~
resul~s
were exneriencea from a men
.,
grams of antifebrine daily for two days in succession
.
'
:Pre,,aration of Samn1e for Analysis . -The samples for
analyses were -nre:nared by dissolving acetanilide in embalming
fluid and treating ground meat with the. so1ution.
Extraction~-Ether
or chloroform will extract acetan-
ilide comnletely from an acia solution. The·method used in
every extraction in this thesis was to weigh out a nortion
of the mixture for extraction and
eva~orate
it to dryness on
the water bath.Dissolve it in as small amount.of water as nossible and then extract the acetanilide with ether.
)
Detection.-After each extraction and purification
several ·of the following tests were. applied to identify it.
22
.,. ... •··, i., ..,. "... "' • ... •"
~~
Indo~henol
,
I
~.
.. .. .•
I
._..
-·"
~
- -- , ..... •
-
.__,,... -
Test.-Acetanilide was boiled with a few
cc.of fuming hydrochloric acid and evanorated to a small volume. Vlhen cool a few cc. of phenol solution and a few d:eo"Ps
Of calcium hynochlorite solution were added.The solution turned violet-red color. Ammonium hydroxide used as a surface
layer made the solution a nermanent indigo-blue color. Acete,nilide also gives the -phenyl isocyanide test.
Calcium Hynochlorite Test.-Boil acetanilide with
alcoholic notassium hydroxide for a few minutes and extract
with ether.This solution will denosit aniline on evanoration.
Dissolve with water and test with calcium hypochlorite.
Analysi.s .-In order to see what effect if any embalming fluid had on acetanilide,a series of ex:periments weee run
with them together. Acetanilide in solution in the embalming
fluid wans then added to ground meat and analyses made at
various intervals.
Data.I.
Samnle containing embalming fluid and acetanilide.Embalming fluid .
Acatanilide,
lOOcc.
0 .. 2 grams.
(a). One half of the sample taken for analysis .
Dish Plus acetnanilide 56·.1485
Dish
56·. 0580
Acetanilide
0.0905
(b). The remainder of solution analyzed 10 days later.
Dish nlus acetanilide
Dish
Acetanilide
55'. 8"400
55'. 7482
0.0818
23
••
-··H ••
··-
•.•••
I I .. ' -..
- . -.. - ....
Sanm1e nrenarea March 84,1920.as follows:
-
.,
'
Embalming fluid
BOcc ..
Ground meat.
80 grams.
o.5 grams
Acetanilide,
'
(a,) .. A,,ril
l.Samnle taken for analysis,40 gra.ms.
Dish nlus acetanilide 34·.3749
Dish
3~.2535
Acetanilide
(b).Anril 16,Sam,,le taken for
0.1214
analysis.~O
grams.
- Dish nlus acetanilide 43·. 6862
Dish
43~6110
Aaetani:lide
· o. 0752
(c) .May 2.,Samnle taken for analysis.BO grams.
Dish nlus acetanilide 36'.6504
"Dish
36'. 4517
Acetanilide
0.1987
III.
Samnle nrenared June
3.1920~as
Embalming fluid,
lOOoc.
Ground meat,
100 grams
.
Acetanilide,
.
.
follows;
.
0.2 grams.
(a)0June 8.Samnle taken for analysis,50 grams.
Dish Plus acetanilide 54·.1698
l>ish
54·.123.4:.
Acetanilide
0.0464(b) .June 20,Samnle taken for analysis,50 grams.
Dish nlus samnle of .Acet 54 .• 171?
Dish
. 54'.1234
Acatanilide
( c). July
..
0.0478
9 .. Samnle taken for analysis. 50 grams.
Dish plus acetanilide 56'.1015
Dish
56·. 0580
Acetanilide
0.0435
24 .
.ANTIPYRINE
Antinyrine . or l-nhenyl-2,3 dimethyl-isonyrazolene,
C1,H,4 0N2 , forms monoclinic crystals having a faintly bitter
taste and melting at 113 degrees.It is soluble in less than
one part of cold water,in about one part of alcohol ,one nart
of chloroform and in 50 narts of ether.
Distribution. -:Part of the antiuylftine in· the organism
annears in the urine as oxy-antinyrine-glycuronic acid and
another
~art
is unchangea in
th~
syatem and can be detected
directly in the urine with ferric chloride solution.It is
easily absorbed and the urine may show a reddish color even
en hour after the drug has been taken.Its detection is nossible
after 36 hours. Jonescu states,that antipyrine in the human
system nasses into the urine unchanged.
Prenaration of Samnle for
Analy~is.-
The samples for
analysis were nrepared by dissolving some antipyrine in the
embalmi~
fluid and then treating some meat with the solution.
Extraction.-Ether or better chloroform.extracts the
antinyrine almost comnletely from alkaline solution. Ether
will extract small amounts from·tartaric acid solution.It
differs from most alkaloids in that it is more soluble in
Water.The method of extraction was similar to acetanilide.
Detection.- To detect antipyrine,the residue after
the evauoration of the ether
extrac~,is
water and the following tests a1)Plied:
dissolved in a little
25
Ferric Chloride Test.- A few drops of ferric chloride solution was added to an aqueous solution of antipyrine.
It produced a deep red color. The color is seen in a dilution
of 1 : 100,000.
Tannie Acid Test.-Tannic acid solution produces a
white precipitate when added to an.aqueous solution of the
antipyrine.
Fuming Nitric Acid. Test.- If a few drops of fuming
nitric acid are added to a little antipyrine solution,a
green color will appear. Vlhen this is heated and another drop
is added, a rea color appears.
Analysis.- The plan of proceedure is similar to the
previous analyses.A
of experiments were run with the
serie~
embalming fluid and antipyrine-. When that series had been run,
another was prepared in which embalming fluid,antipyrine and
ground meat were mixed together.
Data.-
'
I.
,
Sample containing embalming fluid and antipyrine.
Embalming fluid,
Antipyrine,
lOOcc.
0.2 grams.
(a).One half of the sample taken for analysis.
Tiish plus an.tipyrine 54.1970
54.1234
Dish
0.0736
Antipyrine
(b).Dish plus antipyrine with the remainder of sample.
Dish plus antipyrine 54.2130
54.1234
Dish
0.0996
Antipyrine
II.
Sample
pr~~ared
March 19,1920,a s follows:
Embalming fluid,
80cc.
Groung. meat,
80 grams.
Antipyrin e,
0.5 grams.
(a) .March 27, Sample taken for analysis,4 0 grams.
Dish :plus antipyrine 18.9367
18.8272
Dish
0.1095
Anti:pyrine
(b) .:mpril 20,Sample taken for analysis,4 0 grams.
Dish plus antipyrine 87.8578
87.7564
Dish
0.1614
.Antipyrin e
( c) .1.[ay 1, Sam:ple taken for analysis, 40 grams.
Dish plus antipyrine 18.8578·
18.8272 ..
Dish
0.0998
Antipyrin e
III.
Sample prepared June 3,as follows:
Embalming fluid,
50cc.
Ground meat,
Antipyrine ,
5.0 grams0. 2 grams.
(a). June 7, Sample taken for analysis, 25 grams.
Dish plus antipyrine 56-.1005
56.0580
Dish
0.0425
Antipyrin e
(b).June-1 7,Sample taken for analysis,2 5 grams.
Dish plus antipy;rin e 56.1022
56.0580
Dish
O. 0442
Antipyrine
( c) .'.July 6, Sample taken for analysis, 25 grams.
Dish plus antipyrine 56,1919
56.1534
Dish
0.0385
Ahtipyrine
27
CAFFEINE
Caffeine (theine) or 1,3.7-trimethyl-2,6 dioxy-:purine,
c8 H,o0.z NqH,_0,
crystallizes in white shining needles. it is pres-
ent in coffee,tea,coffee beans,cocoa beans and kola nuts.Caffeine is soluble in 80 parts of water,giving a colorless solution with neutral reaction and a faint,bitter.taste.It is not
quite easily soluble in ether. The melting point is 230 degrees.
It is easily soluble in hot water,alcohol and chloroform. It is
a very· weak base and its salts are decomposed by water. The
relations between caffeine and uric acid are similar,which
can readily be seen when its products,formed by oxidizing it
with
po~assium
chlorate and hydrochloric acid,are.compared
with the same products of uric acid.
Absorption.- A very small part of the caffeine taken
into the body passes through unchanged ana appears in the urine.
Most of the
nitrogen of caffeine is eliminated as urea. About
10 per cent appears.in the urine as decomposition products
and the remainder may be cnanged into normal end products of
metabolism.
Prpeparation of Sample for Analysis.-The samples for
analysis were prepared by dissolving some
c~ffeine
in embalm-·
ing fluid and treating finely divided meat with it.
Extraction.-Ether will extract more caffeine from an
alkaline solution than from an aqueous tartaric acid solution.
Since caffeine dissolves with some
diff~culty
in ether but
more easily in chloroform,the latter solvent is used after
the solution has been made alkaline with ammonia.After distil-
28
lation mf the solvent. The caffeine appears in concentric clusters of long,shining needles. From the chloroform extraction
caffeine forms long silky needles arranged in concentric
clusters.
Detecttion.-Having extracted the caffeine,it is very
necessary to. identify the rpoduct.From chloroform extraction
it is usually easy to identify it from the appearance.
Oxidation Test.- pour a little chlorine water over
caffeine and evaporate to dryness u:ppn the water l)ath.
A
brmm residue will remain. If a fev,r drops of ammonium hydroxide solution are added,a fine purple color will appear.
T~nnic
Acid Test.- This reagent,added to an aqueous
solution of carfeine,will give a white precipitate which is
soluble in an excess of acid. This · test iB not characteristic of ca:efeine.
. Analyiss. -The plan of proceedwe here was similar to
the preceding analyses. A series of analyses were run with the
embalming fluid and caffeine and then the two in solution were
added to meat ana analyzed at different intervals.
J)ata. -
I.
Sample coritaining embalming fluid and caffeine
Embalming fluid
Caffeine,
lOOcc.
0 .108 grams.
29
(a). Sample comatningone half of solution analyzed as follows;
Dish plus caffeine
Dish
Caffeine
56. 7999·
56.7481
0.0518
(b).Remainder of sample analyzed 10 days later.
Dish plus caffeine
Dish
Caffeine
54.1735
54.1234
o.o5o1
II.
Sample prepared March 19,as follows:
Embalming fluid,
80co.
Grouna meat,
80 grams.
Caffeine,
1.2 grams.
(a) .March 27 ,Sample taken for analysis,40 grams •
.Dish plus
Dish
ca~feine
Caffein~
36.6538
36.4517
0.2021
(b) .April 27, Sample taken for analysis, 40 grams.
Dish plus caffeine
Dish
Caffeine ·
36.7068
36.4516
0.2552
( c). May_ 4, Sample taken for analysis, 40 grams.
Dish plus caffeine
Dish
Caffeine
44.6522
44.4512
0.2010
30
III.
Sample prepared June 3,1920,as follows:
Embalming fluid,
50cc.
Ground meat
50 grams.
0.19 grams.
Caffeine,
(a) • June 9, Sample taken for analysis, 25 grams.
Dish plus caffeine
Dish
Caffeine'.
56.1005
56.05~0
0.0425
(b).June 18,Sample taken for analyiss,25 grams.
.•
Dish plus 'caffeine
Dish
Caffeine
55.8000
55.'7481
0.0519
( c) • July 8, Sample taken for analysis, 25 grams.
Di~h
D.ish
plus caffeine
Caffeine~
55.'7885
55.'7481
0.0404
31
VERATRINE
Veratrine,C32E~O,,is
an intimate mixture of two iso-
meric alke1oids. These are cevadine,also called crystallized
veratrine,which is nearly insoluble in water,ana amorphous
veratridine which' 1s soluble in water. Veratrine appears as
anwhite amorphous powder. It has a sharp burning taste and
the minutest quantity introduced into the nostrilc cause continued sneezing. It is almost insoluble in hot water,fairly
soluble in ether,benzene and amyl alcohol,and freely soluble
in alcohol and chloroform.
Lethal Dose.- The lethal dose of veratria or of the
pure alkaloids for man are not knovm. Poisonings by veratrum
or its allraloids are of exceptional occurrences. All of the
alleged homicides by veratrum occurred in France.The lethal
dose is probably high. A man took afour teaspoonsful of Norwood' s tincture in two doses,having mistaken the directions,
and recovered.
?reparation of Sample for Analysis.- The samples for
the analyses were prepared by dissolving some veratria in the
embalming fluid and treating ground meat with the solution.
Extraction.-Ether,alcohol or chloroform will extract
veratria from ail alkaline solution which has been prepared
as.in previous
analyses from ground meat.Ether will extract
very little from acid solution.The alkaloid is deposited from
the ether solution as a white,amorphous powder.
Detection.- After extracting the veratria as described, the following tests were a11pl ied to identify it;
Concentrated Sulphuric Acid' Test.- Pour a few drops
of concentrated sulphuric acid upon a trace of veratrine.The
alkaloid will have an intense yellow color which graaually
changes to orange and finally to a cherry red.Heat applied·
gently will hasten the color change.
Froehde's and Erdmann's reagents give color changes
similar to those by sulphuric acid.
Concentr~teft
Hydrochloric Acid Test.-If a few cc.
of concnetrated hydrochloric acid are aaaea to a little veratrine, the solution will be colorless. When heated on the water
bath for a short time a cherry red color willa
ap~ear.
Concentrated Nitric Acid Test.-Concentrated Nitric
acid dissolves veratrine with a yellow color.
Weppem's Test.- Mix some vera.trine with some cane
sugar and then aad a few drops of concentrated sulphuric acid.
At firs.t a yellow color will a1)pear which later turns blue·.
Vitali's Test.•Dissolve some veratrine in fuming
nitric acid and evaporate to dryness· on the water bath.If
the yellow residue is moistened with an alcoholic potassium
hydroxide solution, the color will change to. red or
red-~iolet.
Analysis.-In order to determine the effect,if any,
that embalming fluid has on veratrine,a series of analyses
were run with embalming fluid and veratrine.Vlhen the above
was worked out a series of analyses were 1Tthn with embalming
fluid,meat and veratrine mixed together.
33
Data.-
I.
Sample containiug embalming fluid and veratrine.
Embalming fluid,
Veratrine,
lOOcc.
o. 2 grams.
(a).One half of the sample taken fDr analysis.
Dish plus veratria
Dish
Veratria
56,1419
56.0585
0.0834
(b),The remainder of sample analyzed after 10 days.
Dish plus veratria
Dish
Veratria
56.1395
55·.0585
0.0810
II.
Sample prepared.June 3,1920,as follows.
Embalming fluid,
lOOcc.
Preparea·meat,
100 grams
Veratria,
0.2 grams.
(a). June 9,Sample taken for analysis,50 grams.
Dish plus veratrine 56~0851
Dish
56.0580
Veratria
0.0271
(b).June 16,Sample taken for analysis,50 grams.·
Dish plus veratrine 55.7785
Dish
55.7481
Veratrine '
0.0304
( c) • July 8, Sample taken for analysis, 50 grams.
Dish plus veratrine 54.1569
Dish
54.1234
Veratrine
0.0335
34
STRYCHNINE
Strychnine,C:z,~2-0.:i..N:z:,
the seeds of the Strychnos
is the :poisonous alkaloid of
Nt1X
Vomica,in which it is present
together with brucine •. It crystallizes
in colorless prisms
which melt at 284 degrees. The alkaloid dissolves in 6600
parts
.~f
cold and 2500 :parts of hot water,giving alkaline
solutions having a bitter taste. It is nearly insoluble in
absolute alcohol'and in absolute ether. It dissolves in 150
parts of cold and 12 parts of boiling,alcohol ( 90 per cent.
by volume);it is also soluble in commercial ether and in benzene; but most readily in chloroform. Strychnine diluted with
water l
600,000 can be recog.aized by its bitter taste.
Lethal Dose.-The minimum lethal dose of strychnine
for adults may be placed at about 0.03 grams (half a grain).
That quantity has provea.fatal in two instances,in both.of
which the amount of the dose was accurately fixed.
Absorption-Distribution.-That absorption of strychnine from the alimentary canal begins immediately and that
progress is rapid is shown in numerous cases.strychnine more
than likely stimulates the movements of the stomach.Little
can be learned from the data available as to the exact distribution of the alkaloid in the human system after death.
Preparation of Sample for A:n.alysis.-The samples for
analyses were prepared by dissolving a small amotult of the
alkaloid in embalming fluid and then adding it to a t'ixed
quantity of finely ground li1rer.The amounts of the alkaloids
. 35
used wer.e such that each sample would contain far below the
lethal dose.
(
Extraction.Sodium and potassium hydroxide,ammonia
and alkaline carbonates precipitate the base strychnine from
the aqueous solutions of its salts as a white
A small portion of the
~ample
crysta~line
solid.
for analysis was treated
with water containing a small amount of sulphuric acid and
boiled to dryness on the water bath. The alkaloid
was extract-
ed with water containing a_little·acid from the dried meat.
The fat was separated from the water solution by extracting
with chloroform in acid solution.The strychnine was extracte·"'d
with ether from the solution made alkaline.The ether extract
deposited the alkaloid on evaporation in fine crystalline
needles.
Chlo~oform
takes up the alkaloid more freely,since
strychnine "is more' soluble in chloroform than ether.
Concentrated sulphuric acid,Erdmann's and Froehde's
reagents dissolve pure strychnine without color.Nitric acid
dissolves it with a yellowish color.
Detection.- After each extraction and purification
it
is essential to make a number of identification tests.
Sulphuric acid-Dichromate Test.-Dissolve a ltttle
strychnine in a small amount of concantra.ted sulphuric acid
on a watch glass. A small crystal of potassium dichromate is
then added to the acid containing the strychnine. Intense· blue
36
j
or bluish purple will come from the dichromate when the watch
glass is tilted a little. If the whole is stirreda little
·the whole solution will take on a beautiful evanescent blue
orblue violet which changes to a delicate pink then to a red
and finally to a dirty green.
Analysis.- In order to see if the embalming fluid
has any reaction with strychnine,a sample was run with a small
amount of strychnine in the. fluid. When this sample had been
analyzer another was prepared containing embalming fluid,strychnine and finely graoµnd meat.
Data.Sample containing embalming fluid and
Embalming fluid,
Strychnine.,
(a).
strychnine~
lOOcc.
0.105 grams.
One. half of the sample taken for analysis.
Dish plus strychnine 54.1755
Dish
54.1234
Strychnine
0.0521
(b). The remainder of the sample analyzed
io days later.
Dish plus strychnine 56.1010
Dish
56'. 0580
Strychnine
0.0430
II.
Sample prepared March 19, 1920, as follows:
Embalming fluid,
80cc.
Ground meat,
80 grams.
S "'crychn ine,
05 grams.
37
)
(al.March 24,Sample taken for analysis, 40 grams.
Dish plus strychnine 87.7900
87.6'700
Dish
Strychnine
0.1200
(b) .April 3,Sample taken for analysis,40 grams.
Dish plus strychnine 44.6287
Dish
44.5142
Strychnine
0.1145
(c).April 24,Sample taken for analysis,4o grams.
Dish plus strychnine 44.5765
Dish
44.4611
Strychnine
O.1154
III.
Sample prepared April 29,1920,as follows:
Embalming fluid,
lOOcc.
Ground meat,
100 grams.
Strychnine,
0.1 gram.
(a).May 4,Sample taken for analysis,50 grams.
Dish plus strychnine 36.4572
Dish
36.4367
Strychnine
0.0205
(b).May 12,Sernple taken rli'or 'analysis,50 grams.
Dish plus strychnine 43.6286
Dish
43.6110
Strychnine
0.0176
(c).May 17,Sample taken for analysis,50 grams.
Dish plus strychnine 43.8300
Dish
43.8141
Strychnine
0.0159
38
IV.
Sample prepared June 3,1920,as follows:
Embalming fluid,
50 grams.
Ground meat,
50 grams.
Strychnine,
O.l gram.
(a+.June 8,Sample taken for analysis,25 grams.
Dish plus strychnine 54.1395
Dish
54.1234
Strychnine
0.016l
(b).June 15,Sample taken for analysis,25 grams.
Dish·plus strychnine 54.1500
Dish
54.1234
Stryclmine
0.0266
(c).Suiby 3.Sample taken for analysis,25 grams.
Dish plus strychnine 54.1486
Dish .
54.1234
Strychnine
0.0252.
Special Analysis.In the spring of 1916,Frank Kalusa
of Pittsburg,Kansas was poisoned with strychnine.Dr.F.E.Dains
Department Organic Chemistry,University of Kansas,made an
analysis .at the time and found strychnine in parts of the
liver,stmmach,etc.
Some parts of the cadaver were
ke~t
in a glass bottle
with stopper loose enough to admit air. I made an analysis of
the.parts of the
liver~stomach,larynx,etc.o~
July 6,1920 and
found the following strychnine from ·2o grams of cadaver.
Dish plus strychnine 14.8565
Dish
14.8485
Strychnine
0.0080
BRUCINE
Brucine, C11H;,N 2 O~, is present with strychnine in the
seeds of nux vomica. It crystalliZ$S from dilute alcohol in
transpa~ent,four
sided prisms,containing four moles of water.
The alkaloid dissolves in 320 parts of water when cold and
150 :parts hot. It dissolves in 1.5 parts of alcohol, in 2 parts
of chloroform,and 64 parts of benzene. Brucine solutions have
a very bitter taste and a strong alkaline reaction.It differs
from strychnine in being
d~posited
usually amorphous by
eva~­
oration of its ether solution.
Preparation of Sample for Analysis.- The sample was
pre1)ared by dissolving some bru.cine in embalming fluid and
treating finely ground meat -vvith it.
Extraction.- The method followed was similar to that
for strychnine. Ether , benz.ene or chloroform will extract brucine from an alkaline solution. Evaporation of the ether extract
leaves the brucine in the amorphous state.
Detection.- After_ each extraction,evaporation and
Purification a number of well defined tests were a1Yplied to
identify the product.The
t~10
most used tests are:
Nitri.c Acia .. gtam1ous Chloride Test.-Concentrated
nitric acid dissolves brucine and its salts with a blood red
color. This color is not stable and soon chan:'.!es to a yellowish red and finally to yellow. A fey; drops of freshly prepared
stannous ehloride solution to this yellowish red changes the
color to intense violet.
40
R. Mauch's Modificatiou of Nitric Acid-Stannous Chloride Test.-A little brucine is dissolved in a chloral hytlrate
Solution and mixed with nitric acid. If this solution is added
to concentrated sulphuric acid so that it reamins on the top,
a yelloiuish red to deep red zone will a!Jpear immediately.Ylhen
the upper layer hecomes yellow put some stannous chloride on
the top. A brilliant,intensely violet zone will appear between
the two
u~ped
layers •
.Analysis.-In order to demonstrate what effect it
any embalming fluid vrnula have on 1,rucine alone, the two were
put in solution together and analyzed. Having found that the
embalming fluid does not effect the brucine,then the two
were added to pround meat and analyzea at various intervals.
Data.-.
I.
Sample containing embalimng fluid and brucine.
Embalming fluid,
Brucine,
(a)
lOOcc.
O,l gram.
.One ha1 f of the sample taken for analysis.
Dish plus brucine
Dish
Brucine
54.1550
54.1234.
0.0216
(b). The remainder of sample analyzed 10 days later.
Dish plus brucine
Dish
Bruicine
55.7900
55.7481
0.0419
41.
II.
Samnle -prenarea June 3.1920.as follows:
Embalming fluia
J.OOcc.
Ground meat,
100 grams •
.
0.2 grams.
Erucine
(a.) • June 8, Samnle
taken for analysis,40 grams.
Dish nlus brucine
Dish
::mru<hdne
(b), June
55'.7695
55'. 74'ffil
0.0244
15,Sam-nle taken for analysis,40 grams.
Dish nlus bruoine
Dish
Erucine
( c) • July 3, Sam1:;le
55'. 7700
55·. 7481
0.0249
taken for analysis, 40 grams.
Dish nlus brucine
Dish
Brucine
56'.0819
56'.0580
0.0238
42
ATRORINE
AtrorJine, or d i-Ryosyamine, C17E.23N0.1 ~is found mi the
deadly night shade. It i.s a white crystalline solid which
senarates from dilute
alco~ol
in nrisms. It has a melting
noint of 115 degrees. Atropine is almost insoluble in water
but is easily soluble in alcohol.ether and cbloroform. The
aqueous solution of the alkaloid is alkaline and has a lasting
unuleasant taste. Ii)sen found that atrdrpine is very re·sistant in the presence
o~.
J;"mtrefying material. Even after two
years,he could detect the alkaloid which had been subjected
to the inf,luences of decomposition.
Satatistics.-Accidental and usually non-fatal.intoxications by atro-pine are of quite frequent occurrence.suicidal
or homicidal noisonings by them are very rare.The great majority of cases of poisoning by them are from belladonna which
have.been the result of taking the
take for anothermmed icine
gist.
I.~any
either by mis-
~renaration
or by error on the
~-:art
of the drug-
t
ca.ses,sveral of which proved :Latsl,have resulted
from eating berries,the plants
bein~
frequently cultivated
in gardens.
Lethal Dose.- The smallest quantity of
atro~ine
which
has been 1movm to cause death was 0 .0004 grams. T4e smallest
dose reported to have caused the death of an adult was
0~003
grams administered hyuoaermically in· a mistake for strychnine.
Prenaration of
Sam~le
for Analysis.- The sample for
analysis was -prepared by dissolving a small.amount of the
43
alkaloid in some embalming fluid and.treating finely ground
meat with the solution.
Extraction.-The atrouine is extracted from solutions
by ether ,benzene or chloroform,·made alkaline with sodium
hydroxide or carbonate solution •. In a s1)ecial search for atropine use the sod iurn carbonate and extract
which is a better solvent
purified by
a~sso1ving
.
than
\1!.r1. th
chloroform
ether. The residue should be
it in water ,faintly acidu1.eted with
acetic acid,filtering and washing th acid solution with chlor1
of orm or at her. It should th en be made alkaline rli th ammonia
and extractef1 with chloroform. The residue left from the eva.uoration of the chloroform solution is amornhous and may be
converted into crystals by crystallization fromn alcohol.
netection.- Having evanoratea the soltuion to dryness,
the residue was tested as follows:
Vitali's Test.- Dissolve the alkaloid in ·afew drons
of fuming nitric ao-id and evanorate the· solution to dryness
on the i.7ater bath. Moisten the residue when cold with a few•
drops of
~otssium
hydroxide in absolute alcohol. An evRnes-
cent rnirnle ·will a1~:pear if atropine is -present.
Odor Test.-Heat a little atropine in a dry test tube
until a white van or an-pears. An agreeable otttor will be detectea. Add a little sulnhuric acid and heat until it begins to
darken then dilute with a little Pater. During the faaming
'
I
a svmetish odor of honey ray be detectecl.
44
Ger~ard's
Reaction&-Add a small nortion of the
substance to be tested to a little ·five--per cent solution
of mercuric chloride in 50 ner cent. alcohol and warm gently,
when a yellowish
preci~itate
of mercuric oxide is, formed
which turns a brick red.
Analysis.-A samnle containing embalming
f~uid
and
atropine was thoroughly analyzea.Then embalming fluid.meat
and atrouine were mixed together ana analyzed at various. intervals. of time.
Data . I.
Sam~le
containing embalming fluid
Ernbalmin~
.Atroi:>ine,
(p)
fluid.
·ana
atropine.
lOOcc •
0.1 gram.
.One half of the samnle taken for analysis.
Dish nlus atrouine
Dish
Atropine
55'. 7630
55·. 7481
0.0149
(b). The remainder of sam·nle analyzed 10 days J.ater.
Dish plus·atro~ine
Dish
Atronine
54·.1359
54·.1234
0.0125
45
II.
Embalming fluid.
Groung meat,
Atronine.
·:.60cc.
50 grams:
I
O.l gram.
(a). June 10,Samnle taken for analysis,25 grams •
Dish nlus atropine
Tiish
Atrouine
(b). June
.
54·.1415
54'.1234
0. 0181
21, Samnle taken for analysis. 25 grams.
Dish Plus atropine
Dish
Atropine
55'. 7665
55'. r/4Rl
0~0184
'
(o).JuJ:y 12,Sample taken for analysis.25 grams.
Dish ulus atropine
Dish
Atro-pine
55'. 7 615
55·. 7481
Q.0134
46
ACONITE
Aconite was first suggesteo as a medicine by
Store~
in 1762. Since which 'time several snecies have been used and
found to vary in strength. The Roman
~oet
used the word acon-
i tum in referring to many uoisonous ~lants. The s~ecies at
nresent is use are -pormlarly 1mown as monkshood or wolfbane ~
Aconitine is faintly yellowish
in prisms. Its solubility is slight in
solia.crystallizin~
water:~alcohol
ana
ether.
It is readily soluble in chloroform and benzene. It is easily
hydrolizea by acids,alkalies . or
water at a high temoerature,
.
.
with t~c formation of aconin.benzoic acid and .acetic acid.The
i1ure alkaloid gives no 1movm color reaction.
Sta.ti.sties.- Matthiolus relates two exneriments u"Oon
criminals.one in Rome in 1524 and the other in Prague,under
his own direction.One of the nrisoners died and the other recovered.In more recent times aconitic noisonous cases are of
rare occurrences in
~ranee
England and in the United
ing cases
re~orted
and Germany,but more frequent in
States. Most of the aconitic noison-
in me0ical literature are accidental.Homi-
cidal aconitic nosionings are of rare occurrence.
Lethal Dose.-The lethal dose of pure,crystallized
aconitin is very small. One case is reuorted where a woman
died after taking 0.00175 grams. In considering the lethal
dose of aconite regard must be had for the varying strength
r
of different compounds. Although the maximum medicinal dose
is usually fill?ed at 0.1 gram of aconite,the smallest ·quantity
47
Which we can find referred to as having caused death wasone
third of a teasnoonful of u1·s,::eh.tincture.
Detection.-In the excentional cases in which nortions
of the Plant have been taken, these may be recognized in the
stomach content. In a
~ystematic
analysis of aconite it can be
extracted from an alkaline aqueous solution by benzene or an·
ether-chloroform mixture. One difference in this analysis
ov~r
the nreceding ones is that the aqueous solution containing
aconite haa to be
eva~orated
to dryness on the water bath at
a temperature below 60 degrees. as it is reaa ily hydrol.ized.
It is preferable to evanorate under diminished Pressure,and
to use only acetic acid and sodium carbonate in strictly necessary qua.nti ties in effecting the reaction.
Aconitin does not produce any color reactions as far
as I was able to find,neither could I find any S})eoial chemical test by which it could be identified. It forms nreoinitates with several of the general reagents. The most sensitive
reagent for aconitin is the human tongue. A small quantity
-placea
on the tomP.:ue nroduces the neuuliar tingling or l)rick-
ly sensation. Another method which might be used to identify
it.would be to inject it into frogs or mice. A very minute
t(Uanti ty injected into the frog causes death. A card iogra·ohic
tracing of the hearts action of a frog after poisoning by aconite shows a distinct tetanization of tbe heart muscle.followed
be a neculiar neristaltic action ana final arrest in diastole.
In the 1;resent conuitirtmn of our knowledge, the most that the
48
tox'icnlgi st may ·say in most is that the conditions abservea
are the same as would exist if aconitin were nresent. The
lethal dose being small and this dissemina ted through the
body and in a very large
~art
remmved by vomiting and eli-
minated.ch emical tests usually fail .
.Analysi. s. - A samnle was urenared containing the
embalming fluid and aconite.T his samnle was analyzea to see
what effect the two would have. After analyzing the samule
with the two another samnle was pre1mred for analysis which
contained embalming fluid.grou nd meat and aconite.
Data .. L
Sanrnle containing embalming fluid and aconite.
Embalming fluid.
Aconite.
(a) •. One
lOOcc.
0.02 grams.
half of the samnle taken for analysis.
Dish ulus aconite
Dish
Aconite
56'.0685
56'. 0585·
0.0100
(b). The reaminder of samnle analyzed after 10 days.
Dish nlus aconite
Dish
Aconite
54~.1320
54·.1234
Q.0086
( .
49
.
II.
Samnle nrenared June 3,1920,as follows:
..
Embalming fluid,
~J30cc.
Groung meat.
50 grams
Aconite.,
0.05 grams.
(a.). June 4,Samnle taken for analysis.25
Dish.nlus aconite
Dish
Aconit'e
(b) .June
22~·Smrrple
g~ams.
55'. 7555
55'. 7481
Q.0074
taken for analysis.25 grams.
Dish Plus aconite
Dish
Aconite
56·.0665
56·. 0580
0.0085
( c). July 9. Samnle taken for analysis. 25 grams.
Dish nlus aconite
Dish
Aconite
56.0672
56'.0580
Q.QQ9~
50
(.
COCAINE
Cnca1.ne. C17H.z1NO"f, is· founa in the leaves of the cocoa..
It seuarates out from alcohol solution in colorless nrisms
which melt at 98 degrees.It is not easily soluble in water.
but ts soluble in organic solvents.Cocaine has a bitter taste
when 1)lacea on the tongue ca.uses temnorary. local
It -is easily
anaesthesi~t.
soluble in eJhltier. alcohol, chloroform and benzene.
Dilute acids dissolve cocaine while the alkalies nrecinitate
the alkaloid from • .its solutions of its salts ·,cocaine is usea
medicinally in the form of its chloride.
Lethal Tiose.-In the brief ueriod
durin~
which cocaine
has been in general use.instances of poisoning by it have been
numerous. The quantity taken is stated in only 25 of 67 fatal
cases. A child- died from a dose of Q.024 grams.In three of
five cases in which cocaine was swallowed by adults the amount
taken was more than 1 gram.Much smaller quantities than one
gram may cause death when more directly introduced into the
circulation.
Absorntion-Distribu tion.-Cocaine,even in moderate
doses,stimulates the central.nervous system. A small amount
may be found in the urine and the liver but the greater --rart
seems to be found in the heart.and circulation.
Prenaration of Samnle for Analysis.-The samule for analysis was made by dissolving a small amount of the cocaine in
.
'
embalming fluid and treating meat with the solution.
Extraction.-Ether,c hloroform and benzene will extract
cocaine from an alkaline EJ:qu_eous solutio:ia. }mst of the alka-
51
loid reagents will urecinitate cocaine from very dilute solutions of its ssiss. Cocaine is extracted from ammoniaaal
aqueous solutions by ether after similar treatment as in the
Tirevious extractions.
Pure concentrated sulnhuric and nitric acids,as well
~s
Erdmann's,Froehde's and Mandelin's reagents dissolve the
cocaine without color.
Detection.-Having extracted the cocaine as outlined.
the following.tests were awplied to identify it.
Precinitation Test.-Dissolbe a considerable quantity of cocaine in a few drops of dilute hydrochloric acid
then add potassium hydroxide solution until alkaline.'?hen
coola crustalline })recinitate will anpear.
Pota.ssium 'Permanganate Test.-Add saturates notassiuin
nermanganate solution drop by droD to a.' concentrated aqueous
solution of· cocaine salt. This reagent will give a violet,
crystalline urecir)itate of cocaine nermanganate.
Chromic Acid Test.-Add a few drops of 5 ner cent.
chromic acid solution to a solution of cocaine salt.Each ari:ro
will l)roauce a "!1recipitate which will disan-pear
v~hen
the
solution is shaken. Add to the clear solution a few drops of
concentrated hydrochloric acid which will })reduce an orngge
yellow
~recipitate.
Probably the most characteristic reaction is the
physiologica+ action
in~)roducing
local amaesthesia at the
noint mf anplication on the tongue.
52
Vi tali' s Reaction.- If a small qu·anti ty of cocaine
(0.0000% grams) be moistened with sulphuric acid and a frag -
ment of iodic acid or potassium or sodium iodate be added after
.solution,and the mixture warmed over the water
~treaks
of color are
produced~which
bath~light
change to dark green and
then to deen blue. On stronger heating the liquid becomes
violet and gives off violet vanor.
Analysis.- It was necessary to see what effect,if any,
embalming :Eluidhad on cocaine.hence a series of analyses were
run.with the two together.No action being shown,then the two
in solution were added to finely ground meat and analyses run
at various
~eriods
of time.
Data.-
I.
Samnle containing embalming fluid.and cocaine.
Embalming
Cocaine,
.
.
(a) •
flui~,
LOOcc.
0.0555 grams •
One half of the sample taken for analysis.·
Dish plus cocaine
Dish
Cocaine
54·.1489
54·•.1234
00.0254
(b}.The remainder of the samnle analyzed 10 days later.
Dish -olus cocaine· . 54··.1442
Dish
54·.1234
Cocaine
0.0208
53
I I ..
Samule
~renarea
June
3,1920~as
Embalming fluid.
lOOcc.
Grouna meat.
100 grams
Cocaine,
follows;
0.1 gram.
June 8.
··
(a). Samnle taken for analysis,50 grams.
Dish ~lus cocaine
Dish
Cocaine
55'. 7595
55·. 7481
Q.0114
(b) • June 16, Sa!Il}!le ta ken fo .r analysis, 50 gr ams.
Dish plus cocaine
Dish
Cocaine
56·.0706
56'. 0580
0.0126
( c). July 8 "Samnle ta ken for a.nalys is. 50 grams.
Dish ulus cocaine
Dish
Cocaine
55'.7574
55·. 7481
0.0093
54
CODEINE
Codeine,C17 H17 NO~OCHJ)OH
.the
methyl ether of morTihine.
crystallizes from vYater,or from ether containing water in .
colorless ootahedrons which are. of ten very large. These crystals
are very easily soluble in water. Codeine differs from nost of
the other alkaloids,morDhine for examnle,in its relatively high
solubility in water. Aloogol,ether,amyl alcohol.chloroform
and benzene also dissolve codeine freeley. Aaueous codeine solutions are strongly alkaline and bitter. nure codeine solutions
do not reauce iodic acid.nor does it nroduce a blue color in
a mixture of potassium ferrioyanitfe and ferric chloride solutions. (Differenae between mornhine and codeine.)
~e sym~toms
of codeine noisoning differ materially from those caused by
morDhine.
Extract·ton.- Codeine is extracted from alkaline solutions by benzene.Ether and chloroform dissolve it freely.
Being closely related to mornhine,of which it is the methyl
ether.it resnonds to several of the tests for mornhine.yielding
similar nroducts of decomuosition.
Detection.-Having extracted the codeine and nurified
i.t by redissolving,the following tests were anplied to identify the product.
Sulnhuric Acid Test.-Concentrated sulnhuric acid
dissolves codeine without color, .After long contact or uuon
anplication of gentle heat.the solution will have a readish
to bluish-violet color. The solution of codeine in concentra'
ted sulnhuric aci.d .heated to· 150 degrees and then comlea . is
55
...
'·- .
-.•
•·
·''
...
... ..
-
~
'
... -
....
-- .. '
colored deep red by a dron of concentrated nitric acid.
N:i tri.c Acid Test. -Cold ni trio acid will convert codeine into nit:oD-codeine. At the·same time the acid will dissolve the alkaloid with a yellow.color which soon changes to
red, Concentrated nitric acid dissolves codeine with a reddish brovvn color.
Oxidation Test. - Mtx a. li.ttle codeine uuon a watch glass·
with four times the quantity of finely nowdered nota.ssium
,
arsenate. Add a few drous of concentrated sulnhuric acid and
warm gently. The acid will have a deen blue color,if the
codeine is not lfUite nure. If water or sodium hydroxide sol- .
ution is
added~the
blue color will change to orange yellow.
Froehde's Test.- Thi_s reagent dissolves codeine with
a yellowish color which S?on
ch~ges
to green and finally to
biue. Gently warming the solution will hasten the color change.
Formal in-Sulnhuric Aci.d Test.- Concentrated sul11huric acid containing formalin dissolves coaeine with a reddish
violet color which changes to blue violet. The color is very
nersistent.
Furfurol Test. Dissolve codeine in a few drops of
f
concentrated
sul~huric
acid and warm gently with a dron of
cane sugar solution. This will !lroduce a purnle color.
Pella.iri 's Test"l"Dissolve codeine· in concentrated
hudroohlorio acid and add at the same time a few
dro~s
of
56
....
- - . ...
.
·-~
....
....
.
. .
..· - - .... ~
~
·.. ... ....
~
.,.
-. ... - ....
.
concentrated nitric acedand a few drops of sulnhuric acid. Exnel
the hydrochloric acid on the water·bath.Dissol-ee the dirty
red or violet residue in a few cc. of water and add a little
hydrochloric acid and neutralize with acid sodium carbonate.
Then add alcoholic solution of iodine dro-o by dron with shaking. An emerald green solution indicates codeine. Extract the !: ....
green color with ether and the resulting color will be Eec1.where
A.s the aqueous solution will be green. Both codeine and mornhine will
~ive
this test.
Anal~sis.-The
first uart of the wark was to determi-
ne the effect,if any,of embalming fluid on codeine. A series
of wxoeriments were run with embalming fluid and codeine.
Then a series of analyses were worked out with embalming fluid
and codeine mixed with ground meat.
Data;-
r.
Samnle containing embalming fluid ana codeine.
Embalming fluid.
Codeine.
(a).
lOOcc.
O .02 grams.
One half of the sru1i-nle ta ken for an nlys is.
Dish nlus codeine
Dish
Codeine
5'6'. 06Al
56·.0585
0.0096
(b). The remainder of sample analyzed 10 days later.
Dish plus codeine·
Dish
Codeine
56·. 0705
56'. 0585
o.oum
57
II.
,.
Samnle nreuared June 3,1920,as follows.
Embalming fluid.
50cc ..
Ground meat.
50 grams •
Codeine,
(~).June
.
0 .05 grams •.
7.Sam,,le taken for analysis.25 grams.
Dish plus codeine
Dish
Codeine
54·.1350
54·.1234
0.0107
(b). June 23,.Sam"l')le ta.ken for analysis,25 grams.
Dish -ryJ.us codeine
Dish
Codeine
54·.13ln
54'.1234
0 .0116
( c). July 7,Samnle taken for analysis,25 grams.
Dish 11lus codeine
Dish
Codeine
56·.0675
56'. 0580
0.0095
5g
NARCOTI1TE
Narcdit:tne, CzzRi}W 1 , crystallizes in neeales which are
nearly insoluble in cold water but readliy solublme in boiling
alcohol or chloroform. The se,,aration of· the alkaloid from the
cold alcohol solution is almost
com~lete.
At 15 degrees narco-
tine dissolves in l?O ilarts of ether and 22 uarts of benzene.
Solutions of narcotine are not alkaline nor bitter.In these
resnects narcotine is very different from 01)ium alkaloids.
Prenaration of Samnle for
.AnB..lysis. - The samnles for
analysis were· prenared by dissolving some narcotine in some
embalminp; fluid and then treating finely ground meat with
the solution.
Extraction.-N arcotine is so ·fe·ebly basic that chloroform will extract the alkaloid comnletely from an aqueous
tartaric acid· solution. The
se~aration
of this alkaloid from
all of. the rest .is easy because of this ·fact,natural ly ether
or chloroform will also extract it from an alkaline solution.
The al1raloid as it comes from the ether solution is slightly
colored which changes in time to a crystalline mass .
Detection.-Ha ving separated- the narcotine from the
aqueous· solution as detailed above.the following tests were.
a~plied
to identify the nroduot.
·\
Sul~huric
Acid Test.- Dissolve some narcotine in
.concentrated sulnhuric aoid,a greenish yellow color will
an1)ear which gradually changes to a refldish yellow and
finally after several ·aays to raspberry reD.
59
, .
.,_,'
I
Dilute Sulnhuric Acid Test.- A solution of n·arcotine
in
dilute sulnhuric acid,evanoratea on the Tiater bath has a
rerdish yellow color,changing with heat to crimson red.
Froehde's Reagent.- This reagent dissolves narcotine
with a greenish color. If concentrated Froehde's reagent is
used.the green color changes to cherry red.esuecially afmnr
heating.
Couerbe's Test.- Dissolve narcotine in cold concentrated sulnhuric acid and add a little nitric acid which will
give a red color.
Analysis.- It was necessary to determine if embalming fluid would have any annreciable effect on narcotine
alone,hence a series of analyses were run with those together.
Then a series of analyses were made with
embalming fluid.
ground meat and narcotine.
Data.-
I.
·'
Samnle containing embalming fluid and narcotine.Embalming fluid,
Narcotine·,
(a). One half of the
lOOco.
0 .1~ram.
sam~le
taken for ·analysis.
Dish ·plus narcotine 56'.1040
Di sh
56•. 0580
Narcotine
0~0460
(b).The remainder of solution analyzed after 10 dap:s.
Dish -plus .narcotine 56 .• 0922
Dish
56~0580
Narcotine
0.0~42
6C
II.
Samnle
Tire~ared
June 3,1920.as follows:
Embalming fluid .. ·
Ground
meat.
:Narcotine
(ft). June
150cc.
100 grams.
;
0.225 grams.
10. Sam11le taken for analysis, 50 grams.
Dish nlus narcotine 54·.1600
54 .1234
"Disl1
Narcotine
0.0366
(b)oJune 15,Smnnle ta.ken for analysis,50 grams.
Dish nlus narcotine
Dish
Narcotine
54~1612
54·,1234 .
o.0378
( c). July 6 ~ Se.mnle -: taken for analysis, 50 grams.
Dish 11lus narcotine 55'. 7845
Dish
5fr.?481
Narcotine
0.0364
·G1~
..
· ·····
QUININE
Quinine,GzoRuN~O~,is
containea in cinchona bark unto
3 ner cent.,the yellow bark of Calisaya contains unto 12 ner
cent. The bark is l)OWdered and treated with sul-phuric acid and
from the acid.the bases are preciuitated by adding soda.On
standing the }Jrecinitate becomes crystalline, Anhydrous auinine melts at 173 degrees. An ether solution
o~ eva~oration
denosits the quinine as an amorphous solid. Quinine is soluble
in about 2060 narts cold and 700 parts boiling water and is
freely soluble in alcohol.ether and chl0roform. Solutions of
quinine in sulphuric acid,acetic and tartaric gives a beautiful blue fluorescence. In
acid ·this fluorescence
sul~huric
is visible even to a dilution of l
!
1,000,000. Hydrochloric
acid does not give a fluorescence.
I?re~aration
of the sample for analysis.- .The samnle
for analysis was ·'.lre1}ared by dissolving quinine in embalming
fluid and treating ground meat with it.
A ~ortion for analy-
sis was evanoraterl to dryness on the water bath .and extracted
with aoidulated water.
Extraction.- Ether,benzene or .chlrroform will extract
quinine from an aqueous alkaline solution. Ether on
eva~.ora­
tion denosits the alkaloid as a resinous,amor1)hous varnish .
D~tection.-Having
extracted the
quinine
as
above
suggested,the following tests were applied to identify it.
Fluorescence Test.-Dissolve the residue from the·
ether extraction in a little dilute
is
~res~nt.this
sul~huric
acid. If quinine
solution will give beautiful hlue fluroescence.
62
...
Thalleoqu in Test.- Dissolve quinine in afew drons
of very dilute acetic acid and add a few drops of saturated
chlorine water. The colorless solution has n. faint blu.e fluorescence. An excess of ammonium hydroxide added will give an
emerald green color.
Rera-pathi te Test.- Mix 30 drops of acetic acid,20
d.rops of absolute alcohol and one drop of dilute sulnhuric
acid: A few drops of this to the quinine solution
then heat
to·boiling . Finally add one dron of alcoholic colution of
iodine. Agter some time,if tTUinine is uresent.gr een leaflets
with mmetallic luster will form. This is '"an iodine comnound
of quinine called "Hera11ath i ten.
Hirschcoh n' s Test. - If one drop of each of 2 l)er cent
hydrogen peroxide and 10 l,1er cent. co1)1)ersul1)hate :solution
are added to a neutral solution of quinine at the boiling point
a rasuberry red
to blue
p..nd
color
.ap~)ears.
T}jis color 1vill in time ahange
finally to green. Sensi titre l : Lo, 0'"0 ..
Potassium Bismuthou s Iodide.- Of all the alkaloida l
reagents,u otassium bisrnuthou s iodide is the best as a 11recinitant of quinine. This reagent nrecinita tes quinine having
an intense yellowish red color.
Analysis. In order to determine ·whether the embalmi.ng fluid vrnuld have any appreciab le effect on quinine,a
series of analyses were run vvi th tho two. Th<?n embalming
fluid,quin ine and ground meat were mi:i&:ed together· and analyzed at intervals of a few
days~
63
Data. I.
Sample conatining embalming fluid and quinine.
Embalming fluid,
lOOco.
0.2
Cuinine~
(a)
&
grams~
One half of the sanrnle ana1yzea. gave:
Dish Dlus quinine·
Dish
Quinine
54·.. 1855·
54'.1234
o.os21
(b )., The remainder of solution analyzed after 10 days.
Dish nlus quinine
Dish
Quinine
II.
Sam"Y'lle ·nrenared March 19, 1920 ~as follows:
Embalming fluid.
lOOcc.
Prenared meat.
100 grams.
Q,uinine
1 gram.
'!'
(~).March
24,Samnle take:ri for ana1ys is. 50 grams.
Dish nlus quinine
43·. 6230
43·. 6110
0.,1120
Dish
nuinine
(b) .. Anril 5.Samnle taken for analysis,50 grams.
Dish nlus ouinine
Dish
. Quinine
I
43·, 6986
43·. 6110
0.0876
·( c) .A'l"lril 22, Sam11le taken for analysis, 50 grams .
Tiish T>lus. ouinine
Dish
. ine
.
.,!_u in
(\
44'.5500
44·.4512
0.0988
64
•
<a) •
#
:May 4,Samnle taken for analysis.50 grams.
Dish nlus quinine
Dish
Quinine
36·.5339
36·.4516
Q.0823
III .
•
Samii le preuared June 3.1920 a.s follows:
Embalmin2' fluid •.
LOOcc.
Prenared meat ..
100 grams.
Quinine,
(a)~
0.2
~rams
..
June 8,Sa11J.Y'le taken for anlysis,50 grams.
Dish nlus quinine
Dish
Quinine
(b)., June 17. Samnle taken
56'. 0925
56'.05RO
0.0345
for analysis. 50 grams.
Dish plus ·auinine
J)ish
Quinine
55'. 7900
55'.c!Z48l
Q.0419
( o) ~ Ju1y 8, Sn.mnle taken foranalys is, 50 grams ..
Dish -n,lus quinine
Tiish ·
Quinine ·
56'.1038
. 56'. 0580
0.0458
65
MORPHINE
l,
Morphine..
~17 Hl'IN0 3 ,
is
th~
chief alkaloid contained in
the ehads of non:nies. The a.1kaloids are nresent as sulphates
and meconates. It crystallizes in colorless.rhombic nrisms.
r..a:ornhine is very sr>aringly soluble in cold water,and soluble
in 500
~arts
of boiling water .. These solutions are very bitter
and have a strong alkaline reaction. Crystalline moruhine is
insoluble in ether and benzene. The e.mornhous ai kaloid is soluble in areyl alcohol.hot chloroform· and acetic ether. Soulticnd
of ammonium, l)Otassium and sodium hydroxides and sodium or
notassium carbonate soluitons precipitate free mornhine from
soli.tions of mornhine salts. Mor11hine contains one hydroxyl
groun and one alcoholic grouu and on distillation yields nyridine and quinoline. Its consti tu ti on has not yet been defi-· .
nitely determined.It is easily
oxidized~
Statistics.- The noisonous nature of the penny was
known to the ancients·.iricander (185;;..1.35 B9C.) gives a clear
description of the symntoms caused by
~
poisonous dose of a
"drink -pre1)ared· from the tears which exude from :poppyheads. n
At the ·present time. so far as can be juclgea · from the few
- avt:dlable tables
of statistics,from 35· to 40 I>er cent.of all
accidental ana suicidal l)Oisonings are by opiates.
~~any de~ths
found among children are due largely to the use of various
.
arugs containing 01)iates to soothe the chil d .. Homicidal
'
-poisonings by moruhine ha.ve rarely been the subject of investigation, a fact for which no cause has been assigned.
66
.
·.
'
Lethal Dose.-The effect of a given dose of mornhine
will vary within wide limits under different conditions of
age and physical condition of the individual,and uarticularly
with the extent of previous use. The minimum lethal dose
fo~r
a healthy adult,not habituated to moruhine,is probably 0.2 to
0.26 grams of mornhine. These quantities have proved fatal
in several reported instances.
Absorption.- In the
g:ea~~t
majority of cases of nois-
oning by mornhine,absorution has occu:t±ed·by the alimentary
canal.That absorntion takes naace by the buccal,nasal and
resuiratorY. mucuous membarnes. is shown in· the case of a girl
who was poisoned 'by l'.)utting up mor-phine tablets in a nlant.
Absorntion nroceeds slowly in the stomach has 'peen µroved. M
Marauis found that mornhine disanuears very quickly from the
blood·but is firmly retained by certain organs like the barain.
He also foundthat more than 30 n.er cent, of morphine injected
into·the system was found in the liver in the course of 15 minutes .]for-ohine is oui te resistaiit to })Utrefac tion. Autenrei th
detected mornhi11e nositively in animal material containing the
alkaloid which had stood for 15 months in a glass vessel ana
hac1 com1:1letely nutrefied in ·nresence of insufficient air.
Extraction. The solution containing morphine is made
alkaline wimmmonium,uotassium and
carbonate
smu~ion
s~dium.
hydr9xide or sodium
of morphine salts,and extracted with amyl
alcohol.hot chloroform er acetic 'ether.
6'7
~• ..
--· -
~.
'·•
·-· ·-"'.
I
.,., .
Detectton. -Having extracted the h1ornhine and :purified
it by re-extraction .the following tests were annlied to
·,
identify the
PD~oduct.
Nitric Acid Test.- Concentrated nitric acid dissolves
..
mDnhine with a blood red color Vlhich changes to yellow. st~.n­
nous chloride will not restore the violet color of a solution
that has become yellow. ( distinction from brucine.)
Husemann' s Test.- Dissolve mornhine on a vvatch glass
in a few cc. of concentrated suluhuric acid.The solution is
colorless. Reat on a water bath for some time when a reddish
color wil2 appear. When cool
ass a few dro1)s of ni trio acid
when a rerldish eviolet color
a~Ypears
changing to blood red of.
yellowish red tint.
Pellag-r1's Test.-Proceed as desribed fro codeine.Avoid
excess.of alcoholic iodine solution.
Froehde's Test. This reagent dissolves mornhine with
a violet color which passes to a blue and then to a airty green
and finally to a faint red. These colors vanish on the addition
of water.
FormA.1 in-Su111huric .Acid Test·· The solution used for
this :best is called Marnuis' reagent. }Ji.th
R.
trace of mornhine
it produces a nutnle red color which changes to violet and
finally blue.
~
I-die Acid Test.- Shake a solution of morphine in
dilute sulnhurio acid with a few
dro~s
of iodic acid and
chloroform.M orrhine will liberate iodine-which will dissolve in chloroform with a violet color.
68
;,
Ferric Chloride Test.-Add a few drous of ferric chloride solution to a neutral
mor~hine
solution. A blue coloE an-
1Jears. Prussian Blue Test.- Ada a few drops of a dilute mixture of ferric chloride and -potassi_um ferricyanide solution
to a mornhine salt .solution.A deen blue color
Silver
Test~-Warm
a~~ears.
a mornhine salt solution with
silver nitrate and an excess of ammonium hydroxide solution,
Mgruhine riroduces a gra"i}: nreci1)itate of metallic silver.
I
Bismuth
Test~-
Dissolve mornhine in concentrated
sulnhuric acid ·and snrinkle a little bismuth subnitrateo on
the
surface of the solution., A dark brown color a1')nears.
General Alkaloidal reagents. -The reagents of thrum
c~ass,esTiecially
sensitive towards solutions of mornhine
salts are:
Iodo-~~tassium
Iodide
~hosnho-tunhstic
acid
Potassium mercuric idoide
Potassium bismuthouE iodidie
Phosnho-moly bdic acid
gold chloride.·
Analysis. - It was first necessary to see if embalming
fluid alone y;ould react ·with mornhine • Analyses were maae in
hhich
morphine was dissolved in embalming fluid.There being
no a-nnrecialble effect.the two in solution were nlaced on
some finely ground meat and analyses macle at different times ._
five .fifteen and th,rty days.
69
... 4•
.....,
'/.
Data,-
-.
Samnle con$aining embalming fluid and mornhine.
Embalming fl. uid,
10000.
0.05 grruns.
.
(a). ~one half of the samnle taken fo~.. analysis ..
· Dish ulus mor'l"hine
D~sh
(b)~The
-
55'. '7669
55'. '7481
MoDnhine
0~01R8
remainder of samnle analyzed after 10 dayse
···'
Dish ""'lus mor-nhine 56·.QR02
56·. 0580
Dish
]fornhine
0.0~22
II.
Samiile ·ore1'ared June 3.1920 as follows:
Ernbalmitj.g fluid
Ground meat,
1fornhine,
'.J
50
CC'e
50 grams.
0.1 gram
(a). June 10, Samnle taken for analysis. 25 grams .
.
Dish nlus mornhine
Dish
Mornhine
.
56'.0785
56·. 0580
0.0205
(b) .. June 21. Samnle taken for analysis. 25 · grams.
Dish nlus
Dish
Mor11hine
Mor~hine
56'. 0'7 45
56·. 0580
Q.Oi65
(o),, July 12,Samnle taken for analysis.25 grams.
Dish 11lus moruhine
Dish
56·. 0802
56< 0580
0 .. 0222
170
ARSENIC
!
Arsenic Tri.ox1 de is the common arsenic of the sho,,s.
Aqueous solutions of
arsenci trioxide are acid in reaction.
and probably contain the true arsenious acid. It is r.ead ily
reduoea.with the separation of elementary arsenic,when heated
with hydrogen,carbon or other reaucing agents.
Although the
taste of white arsenic has been determined and described as
hot,acrid,sweetish.metallic and rough, it is under the most
favorable circll!llstances faint. unfortunately it ·is not -possi. ble to assign any definite solubility to arsenic even in water.
as it varies with many conditions. Under al1. circumstances nure
water at ordinary
tem~eratures
dissolve the oxide slowlY, and
leaves a nortion undissolved.
statistics. -Whi. te arsenic, ·,;hich wag -Prenared in the
third century . has in .the nast causea more destnuction of life
than any other l)Oison, excent opium ana its derillatives. The
first homicide
recorded was in 1384. In the United States,we
are under the imnression that ·arsenic holds the. first 1)lace
in the
frequency~of
criminal
administration~
Lethal Dose.-The question:"What is the smallest.quanti ty of arsenic cr:.1::iabl.e of destroying human life?" is one
which has been askea of exnerts in every trial for murder by
arsenic. The ouestion is still without a satisfactory answer.
The answer usually given 1)laces the minimum lethal dose at
between two ana four grains (o.13 -0.26·grams.)
Absorntion.- Al though arsenic may be absorbed into
'o
71
- . ·- ...... __ .. - "..... - ....... . the circulation through every nossible avenue of entrance, it
.,
·"'
...
~.·····~
-
.....
~
.
. ~·
.,..
is chiefly through the alimentary canal that toxicology has
to deal.
begins at once when taken into the stomach.
Absor~tion
It makes its
au~earanoe
in the blood in a few minutes, and is .
soon excreted by the kidneys.
Distribution.-It was from the liver, suleem~1kidnp·sy"
lungs, heart, and muscles that the analysts have obtained the
arsenic. It varys in aifferent organs in different cases.It
os quite -possible that an accumulation of results obtained from
analyses ma.de under
vary~ng ~onditions
may show that there
exists constant differences in the relative distribution of
arsenic in different organs,due to variation
in the time of
introduction, the form of combination, the number and amount
of the dose,or of the habituation of the individual,which
are sufficient marke(1 to enable. the toxicologist of the future
to
})OSi tively
answer questions concerning those l')Oint.
S, but·
the results· hitherto obtained are neither sufficiently cone oraant nor sufficiently numerous to afford ('reliable standards
of comparison. The nresent 1mowledge of the ouantitative ais~
~
'
....
tribution· ·of arsenic in the different tissue and organs of
the body after death caused by arsenic rests unon a small number of more or less comnlete analyses,in cases of -poisoning
in human subject,and
upon the result of, ex1rnriments m)on animals .
.....
Analytical.- I uc;ed two methods in digesting tho 1Jarts
.
.
of the remains of Ed Bunch, T. incoln, K['nsas, who was noisoned
1
with 1)oisonous fly -paJ;er. The methods ar.e as follows:
.
'
'
i. The method suggested by nr.F.13.])ains -r1hich depends
m;on the disintegration action of suluhuric a.cid and nitric
acid:
nla.ced
liter~
~no
grams of the hashed stomach, liver and kidneys were
into a large
eva~orating
dish of the canaci ty .of a
60cc. of nitric acid were added,and the material heated
moderately. The acids were arsenic free. The
uefied gradually and assumed an orange
substance
lia-
tin~~
when this occurred the dish was removed from the water bath
and 10 cc. of sul-phuric acid were added,,.when the mass becomes
brovm aand is strongly attacked,it was· heated until fumes of
Sul11huric acid
wer~
given of:f,1·.rhen a few cc.of nitric acid
were added. The mass again becomes liquid and gave off abundant nitrous fumes. ?/hen all of the acid had been aaded the me.ss
was heated to the beginning of carbonization. Finally the c.arbb:daceous residue was nulverizea ana extracted with boiling
water,
II. Method of Fresinius and von Bobo.- 200 grams of
hashed material consisting of "!)arts of the stomach.liver and
kidneys of Ed Bunch were ulacef] in a flask and 40cc. of arsenic free hydrochloric acid and 4 grams of uotassium chlorate
were added. The mixture was Placed on the water bath and heated
wroth frequent agitation and
occasional addition of potassium
chlorate, until the contents of the
r.Ela~k
were yellow and fluid,
exce'Pt fro fatty ana white granular mattelft in suspension,ana
until the liquid does not darken after heating for half an
hour v;without the adaition of chlorate. The quantity of both
acid and 8Chlorate use(l should be
ke~ot
to the minimum. 7Jhen
73
the disorganizat ion is
com~lete,the
excess of chlorine is ex-
!)elled by passing a ra-oid current of carbon a ioxide through
I
the cooled liquid. The solution was then filtered through a
moistened filter l)aDer and the residue
washed with hot \vater.
Detection.-Ha ving disintegrated the narts of the
caa~wer,
it remained to detect arsenic. The following tests
were used:
Reinsch Test.- The solution abtainea,as arscribed
above'! was ac idula tea in i;art Yvi th about one fifth its volume
of hydrochloric acid ana. heated helow the temnerature of
boiling water in the nresence of metallic coTrper, a gray stain
was f'ormea unon the co1)per from ho th
aisintegra tions.
Marsh Test. - This the mast delicate and most reliable
test for arsenic,was avpliea to both disintegrated narts
as
described above. Nascent hydrogen was generatea by the action
of arsenic free sulnhuric acid on chemically -pure zinc and passea through a calcium chloride tube into a
~iece
of nirex glass
tubing draYm down to a small diameter at one point. When the
hydrogen gas had driven 01'.lt all of the air, the filtered 1.iquia
was intr0duced into the generator through a funnel tube. A
flame was 1)lacea under
the Pirex gamss tubing in front of the
narrow nlace in the tube. An arsenic mirror.becam e visible in
a very fe\v minutes after
~he
introduction of the material and
increased in size and became more lustrous as time passed .
74
. '
Poi.son Fly Paper
;
Fly na:ner.- Ea Bt.mch was 1)0isoned with arsenic extr9,-
..
cted from fly naper. I made a,n analysis of fly paner obtained
frommthe same source as that used for the :poisoning of l[r, and
Mrs.Bunch. I extracted the naner with cold water,another nortion vlith hot water and also comnlete
Data.-
I
Rectangular fly pa uer , YJ'e igh ing
-
'
.
(a)~Extractea 0~5193
extraction with HCl.
1 . 9 8 7 8 grams .
grams of above with cold water.
Weight Gooch Crucible '\j1us As 7 S3 l3. 5443
13·. 5359
Weight arsenic tri-sulphide
0.0084
Weight crucible .
..
O.OOA4 x 0.8042 -::::0.0067 grams
As~0 3 extract
0.0258 Rrams total extract cold water ner
by cold water
paTier~
Boil.ed Panerleft from cold water extract with HCl .
Gooch Filter
Gooch filter
nl~s As~S 3
As,,__8 3
0 ._0633
13·. 5992
13·. 5359
0.0633
0.8042::::. e.0509
gms.R61 extracted from·nart.
\.
x
0.1943 grams ner
~a~er
'
.
HCl extractea after cold water extract.
0.1943 gm. by HC1~+ 0.0258 gips. by cold water_ 0.2201°
grns.a,,a
.
total in one paner.
II.
($.). Extracted 0.5850 grams Yvith boildmg water.
Gooch crucible.plus As-:a.-S 3
Gooch crucible
As.,_.S 3
0<10106
x
0.8042
~
13·.5465
·13'. 5359
Q.0106
0.0086 grams extracted.by hot water nart.
0.0592 grams hot water extract from one nauer.
75
I I I ..
Round Fly Parier
Weight 1. 4065 grams.
(a) Extracted 0.6754 grams of whole with HCl.
Weight Gooch filter .11lus
tl
As~S 3
o. 0565
1f
"
3 13·. 5924
As~S
.
13·. 5359
o.o56n-
x 0. 8042 --=:- O. 0455 grams extract As,_ 03 by HOl.
0. 0955 grams Asi- 03 in each ro1llld. fly pai)er.
An""reciation.In conclusion
I
wish to exnress
my anureciation to Dr.F.B.Dains for his many helDful sug-
gestions auring this work.
Chemical Laboratories.
University of Kansas,
July 23,1920c